The design and execution of reliable complexity enhancing chemical transformations continues to be a goal at the forefront of synthesis. Since transition metal catalysts increase efficiency and enable new routes to complex molecules, their utility will continue to grow. This proposal outlines a research plan for developing a broad class of metal catalyzed reactions that utilize electrophilic metal catalysts (Pt, Au) to initiate, propagate, and terminate cation-olefin reactions (CORs), the principal C-C bond (and ring) forming reaction in terpene biosynthesis. The first Specific Aim focuses on the development of asymmetric catalysts for the dehydrogenative cation-olefin cyclization reaction, with a special emphasis on alkene terminated examples. The second Specific Aim takes this concept one step further by oxidatively intercepting the intermediate Pt-C3 organometallic to generate C3-oxygenated products, which are common bio-active compounds. The third specific aim investigates the mechanism of common Gold(I) catalyzed reactions to support new approaches to asymmetric catalysis and cyclization/cross-coupling. PUBLIC HEALTH RELEVANCE: This project will develop new approaches to the synthesis of complex carbocyclic structures. The emphasis is on discovering synthetic catalysts that mimic the outcome of terpene cyclase enzymes in biosynthesis. Success will provide access to natural bioactive compounds and non-natural analogs thereof.